Cyan dye for ink-jet

ABSTRACT

The present invention relates to a phthalocyanine colorant characterized in that it has, as substituents, at least one unsubstituted sulfamoyl group and at least one substituted sulfamoyl group, the total number of these groups being 2 to 4, and the unsubstituted sulfamoyl group and the substituted sulfamoyl group are bonded to the phthalocyanine ring at the β-position. Said phthalocyanine colorant is suitable for use in an ink, especially a cyan ink, for an ink-jet printer. A printed matter obtained by printing with said ink is excellent in light fastness, ozone fastness and moisture fastness.

TECHNICAL FIELD

The present invention relates to a phthalocyanine colorant, an ink, anink set, an ink-jet recording method using the ink or the ink set, acolored product and a method for producing the phthalocyanine colorant.

BACKGROUND OF THE INVENTION

Lately in the field of an image recording material, particularly, amaterial for forming a color image has been prevalently used, includingspecifically such as an ink-jet recording material, an image recordingmaterial of heat-sensitive transcription type, a recording materialusing an electronic photography method, a silver halide photosensitivematerial of transcription type, a printing ink and a recording pen. ForLCD and PDP in a display field and for electronic parts of CCD in thefield of a movie camera; a color filter is used. In these color imagerecording materials and color filters, to reproduce or record afull-colored image, a colorant (dye and pigment) of so-called threeprimary colors in an additive color-mixing method or a subtractivecolor-mixing method is used. At present, however, a colorant havingabsorption characteristics to realize a desirable color-reproducingrange and fastness to various conditions of use is not actuallyavailable and improvement is strongly required.

An ink-jet recording method has rapidly become prevalent and isdeveloping further because of an inexpensive material, high-speedrecording capability, low noise in recording and easy color recording. Amethod for ink-jet recording includes a continuous method to sprayliquid droplets continuously and an on-demand method to spray liquiddroplets according to an image information signal. A method fordischarging the liquid droplets includes such as a method fordischarging liquid droplets by pressurization using piezoelectricelements, a method for discharging liquid droplets by generation ofbubbles in an ink by heating, a method for using an ultrasonic wave anda method for sucking and discharging liquid droplets by staticelectricity force. An ink suitable for ink-jet recording includes, forexample, a water-based ink, an oil-based ink and a solid (melt type)ink.

A colorant to be used for the ink suitable for such ink-jet recording isrequired to have high solubility or dispersibility in a solvent, to becapable of high-concentration recording, to have good hue, to havesatisfactory fastness against light, heat and an active gas (forexample, an oxidizing gas such as NO_(x) and ozone, and SO_(x)) in theenvironment, to have superior fastness against water and chemicals, tohave good fixation on a recording material with little blurring, to besuperior in shelf life as an ink, to be free from toxicity and furtherto be available at a low price. In particular, such a cyan colorant hasbeen strongly desired as has good cyan hue, along with excellent lightfastness (durability to light), ozone fastness (durability to ozone gas)and moisture fastness (durability under high humidity) and free frombronze phenomenon (also called bronzing phenomenon). Bronze phenomenonmeans phenomenon that a colorant glares like metal chips on the surfaceof a glossy paper, and the like caused by colorant association orinsufficient absorption of an ink. This phenomenon impairs gloss, printquality and print concentration.

Typical structure of a water-soluble cyan colorant to be used for an inksuitable for ink-jet recording include phthalocyanines andtriphenylmethanes. A typical phthalocyanine series colorant reported andused most widely includes the following phthalocyanine derivativesclassified into the following A to H.

A: A known phthalocyanine series colorant such as Direct Blue 86, DirectBlue 87, Direct Blue 199, Acid Blue 249 and Reactive Blue 71. [forexample, Cu-Pc-(SO₃Na)m: a mixture wherein m=1 to 4].

B: A phthalocyanine series colorant disclosed in JP Laid-Open No.190273/1987 (Literature 1), JP Laid-Open No. 138511/1995 (Literature 2),JP Laid-Open No. 105349/2002 (Literature 3) and the like [for example,Cu-Pc-(SO₃Na)m(SO₂NH₂)n: a mixture wherein m+n=1 to 4].

C: A phthalocyanine series colorant disclosed in JP Laid-Open No.171085/1993 (Literature 4) and the like [for example,Cu-Pc-(CO₂H)_(m)(CONR₁R₂)_(n): m+n=0 to 4].

D: A phthalocyanine series colorant disclosed in JP Laid-Open No.140063/1998 (Literature 5) and the like [for example,Cu-Pc-(SO₃H)_(m)(SO₂NR₁R₂)_(n): m+n=0 to 4; and m≠0].

E: A phthalocyanine series colorant disclosed in JP Laid-Open No.515048/1999 (Literature 6) and the like [for example,Cu-Pc-(SO₃H)_(l)(SO₂NH₂)_(m)(SO₂NR₁R₂)_(n): l+m+n=0 to 4].

F: A phthalocyanine series colorant disclosed in JP Laid-Open No.22967/1984 (Literature 7) and the like [for example,Cu-Pc-(SO₂NR₁R₂)_(n): n=1 to 5].

G: A phthalocyanine series colorant disclosed in JP Laid-Open No.303009/2000 (Literature 8), JP-A-2002-249677/2002 (Literature 9) and thelike [a phthalocyanine compound with substituents at controlledpositions, a phthalocyanine series colorant with substituents at theβ-position: On the β-position, see description at the later section].

H: A phthalocyanine series colorant having a pyridine ring disclosed inJP Laid-Open No. 34758/2003 (Literature 10) and the like.

A phthalocyanine series colorant used prevalently today and representedby Direct Blue 86 or Direct Blue 199 is characterized by having superiorlight fastness to a generally known magenta dye or yellow dye. Aphthalocyanine series colorant gives a greenish hue under acidicconditions, and thus is not very preferable as a cyan ink. Therefore,when these dyes are used as a cyan ink, it is preferable to use themunder neutral to basic conditions. However, even when an ink is used inneutral to basic conditions, hue of a printed material possiblyundergoes a big change on an acid recording paper.

Moreover, an oxidizing gas such as a nitrogen oxide gas and ozone thatis often writing up lately as an environmental issue causes the color tochange to a greenish hue and to fade, and optical density of printing todeteriorate.

On the other hand, a triphenylmethane series dye is much inferior inlight fastness, ozone fastness and moisture fastness although its hue isgood.

With increase in application field being used in a display such as anadvertisement in the future, leading to more chances of getting exposedto light and active gases in the environment, such an inexpensivecolorant and ink will be more and more required as has good hue andsuperior fastness against light and an active gas (for example, anoxidizing gas such as NO_(x) and ozone, and SO_(x)) in the environment.However, it is difficult to develop such a cyan colorant (for example,phthalocyanine series colorant) and a cyan ink as satisfies theserequirements at a high level. Although a phthalocyanine series colorantswith active-gas fastness have been disclosed so far in the aboveLiteratures 3 and 8 to 10 and JP Laid-Open No. 80762/2002 (Literature11), such a cyan colorant and a cyan ink have not yet been obtained ascan satisfy all qualities such as hue, light fastness, ozone fastnessand moisture fastness and be produced at a low cost. Accordingly, marketrequirements have not yet been satisfied sufficiently.

A subject of the present invention is to solve the above conventionalproblems and attain the following object. Specifically, an object of thepresent invention is to provide a novel phthalocyanine colorant that hasgood hue as a cyan ink and is superior in light fastness, ozone fastnessand moisture fastness, an ink suitable for an ink-jet using saidphthalocyanine colorant and an ink-jet recording method.

DISCLOSURE OF THE INVENTION

After studying in detail phthalocyanine series colorants having goodhue, excellent light fastness and ozone fastness, the present inventorshave found that the above problems can be solved by using a specificphthalocyanine series colorant as a colorant for an ink and thus havecompleted the present invention. In more detail, the present inventionrelates to a metallo phthalocyanine colorant represented by Formula (1)as shown below, having both a substituted sulfamoyl group and anunsubstituted sulfamoyl group at a specific substitution position(β-position: to be described later), and the present inventors havefound that said colorant has good cyan hue and like and is superior inlight fastness (durability to light), moisture fastness (durabilityunder high humidity) and also ozone fastness (durability to ozone gas)and have completed the present invention. The present invention will bedescribed in detail hereinbelow:

1. A phthalocyanine colorant represented by Formula (1):

[in Formula (1), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide, or a metal halide; R₂, R₃, R₆, R₇, R₁₀, R₁₁,R₁₄ and R₁₅ each independently represent an unsubstituted sulfamoylgroup represented by Formula (2), a substituted sulfamoyl grouprepresented by Formula (3), or a hydrogen atom, provided that at leastone of R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅ is an unsubstitutedsulfamoyl group, and at least one thereof is a substituted sulfamoylgroup represented by Formula (3); and R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ andR₁₆ represent hydrogen atoms; the sum of a number of an unsubstitutedsulfamoyl group and a number of a substituted sulfamoyl group is 2 to 4,and a number of an unsubstituted sulfamoyl group is 1 to 3 and a numberof a substituted sulfamoyl group is 1 to 3.]:

[in Formula (3), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heterocyclic group, and a substituted or unsubstitutedalkenyl group; R₁₇ and R₁₈ may form a ring by bonding together exceptwhen both R₁₇ and R₁₈ represent a halogen atom; and at least one of R₁₇and R₁₈ has an ionic and hydrophilic group as a substituent.]

2. The phthalocyanine colorant according to the above 1, wherein Formula(1) according to the above 1 wherein M is Cu, is represented by Formula(4):

[in Formula (4), R₁ to R₁₆ mean the same as in Formula (1)].

3. The phthalocyanine colorant according to the above 1 or 2, wherein ineach of combinations of R₂ and R₃, R₆ and R₇, R₁₀ and R₁₁, and R₁₄ andR₁₅, one member of each combination is a hydrogen atom, and the other isan unsubstituted sulfamoyl group represented by Formula (2), asubstituted sulfamoyl group represented by Formula (3) or a hydrogenatom, and among R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅, at least one isan unsubstituted sulfamoyl group and at least one is a substitutedsulfamoyl group represented by Formula (3).

4. The phthalocyanine colorant according to any one of the above 1 to 3,wherein R₁₇ and R₁₈ each independently represent a hydrogen atom, analkyl group (which may be substituted with a substituent selected from agroup consisting of a sulfonic acid group, a carboxyl group, a hydroxylgroup, an alkoxyl group, a dialkylamino group, an arylamino group, anaryl group, a halogen atom and a cyano group), a phenyl group (which maybe substituted with one or more a substituents selected from a groupconsisting of a sulfonic acid group, a carboxyl group, a hydroxyl group,a dialkylamino group, an arylamino group, an acetylamino group, a ureidogroup, an alkyl group, an alkoxyl group, a nitro group, a cyano group, aheterocyclic group and a halogen atom), a naphthyl group (which may besubstituted with a sulfonic acid group or a hydroxyl group), a benzylgroup (which may be substituted with a sulfonic acid group) and aphenethyl group (which may be substituted with a sulfonic acid group).

5. The phthalocyanine colorant according to any one of the above 1 to 3,wherein R₁₇ is a hydrogen atom, a carboxyl(C1 to C5)alkyl group, a (C1to C5)alkyl group, a hydroxyl(C1 to C5)alkyl group and a sulfo(C1 toC5)alkyl group; and R₁₈ is a phenyl group having a sulfo(C1 to C5)alkylgroup, a carboxyl(C1 to C5)alkyl group, a sulfonic acid group, acarboxyl group or a hydroxyl group, a benzotriazolyl group substitutedwith a phenyl group having a di(sulfo(C1 to C5)alkyl) amino(C1 toC5)alkyl group, a sulfonic acid group, a carboxyl group or a hydroxylgroup, a phenyl group, substituted with a benzotriazol group having asulfonic acid group, a carboxyl group or a hydroxyl group, a naphthylgroup having a sulfonic acid group or a hydroxyl group, a uracil grouphaving a sulfonic acid group, a carboxyl group or a hydroxyl group, atriazol group having a sulfonic acid group, a carboxyl group or ahydroxyl group, a thiazolyl group having a sulfonic acid group, acarboxyl group or a hydroxyl group, a benzothiazolyl group having asulfonic acid group, a carboxyl group or a hydroxyl group, a pyridinegroup having a sulfonic acid group, a carboxyl group or a hydroxylgroup, and a benzimidazolyl group having a sulfonic acid group, acarboxyl group or a hydroxyl group.

6. The phthalocyanine colorant according to the above 1, wherein contentof the colorant represented by Formula (1) is at least not less than 60%based on total colorants.

7. The phthalocyanine colorant according to any one of the above 1 to 5,wherein the colorant represented by Formula (1) is obtained bysubjecting the phthalocyanine colorant represented by Formula (5):

(in Formula (5), respectively, M represents a hydrogen atom, a metalatom, a metal oxide or a metal halide; L represents a proton, analkaline metal ion, an alkaline earth metal ion and an onium ion of anorganic amine or ammonium ion; and a, b, c and d are 0 or 1, providedthat the sum thereof is an integer of 2 to 4)

or a salt thereof to reaction with a chlorinating reagent to convert asulfonic acid group to a chlorosulfonyl group and subsequent reactionwith an amidating reagent in the presence of an organic amine.

8. A phthalocyanine colorant obtained by subjecting 4-sulfophthalic acidderivatives themselves to reaction in the presence of a metallocompound, followed by subjecting thus obtainedsulfometallophthalocyanine compound or a salt thereof to reaction with achlorinating reagent to convert a sulfonic acid group to achlorosulfonyl group and subsequent reaction with an amidating reagentand an organic amine.

9. An ink characterized by comprising the phthalocyanine colorantaccording to any one of the above 1 to 8, as a colorant component.

10. The ink according to the above 9, wherein an organic solvent iscontained.

11. The ink according to the above 9 or 10, which is used for ink-jetrecording.

12. An ink set characterized, in an ink-jet printer using not less than2 kinds of cyan inks with different colorant density, by using, as atleast one kind therefore, the ink according to any one of the above 9 or11.

13. An ink-jet recording method characterized by using the ink accordingto any one of Claims 9 to 11 or the ink set according to the above 12,in an ink-jet recording method wherein the recording is carried out ontoa recording material by discharging ink droplets in response torecording signals.

14. The ink-jet recording method according to the above 13 wherein therecording material is an information transmission sheet.

15. Then ink-jet recording method according to the above 14 wherein theinformation transmission sheet is a surface treated sheet having an inkimage receiving layer containing white inorganic pigment particles on acarrier.

16. A container containing the ink or the ink set according to any oneof the above 9 to 12.

17. An ink-jet printer having the container according to the above 16.

18. A colored product colored with the ink or the ink set according toany one of the above 9 to 12.

19. A method for production of a phthalocyanie colorant characterized bysubjecting 4-sulfophthalic acid derivatives to reaction with themselvesor subjecting a 4-sulfophthalic acid derivative to reaction with aphthalic acid (phthalic anhydride) derivative in the presence of acopper compound, followed by subjecting thus obtained compound or a saltthereof to reaction with a chlorinating reagent to convert a sulfonicacid group to a chlorosulfonyl group and subsequent reaction with anamidating reagent and an organic amine.

20. A phthalocyanine colorant wherein, in the phthalocyanine colorantrepresented by the following general Formula (9):

(wherein M represents a hydrogen atom, a metal atom, a metal oxide, ametal hydroxide or a metal halide; l includes 0 and smaller than 1; m isnot smaller than 1 and not larger than 3.7; n is not smaller than 0.3and not larger than 3; sum of l, m and n is not smaller than 2 and notlarger than 4; R₁₇ and R₁₈ each independently represent a hydrogen atom,a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heterocyclic group, and a substituted or unsubstitutedalkenyl group; R₁₇ and R₁₈ may form a ring by bonding together, providedthat except when both R₁₇ and R₁₈ represent a hydrogen atom; and atleast one of R₁₇ and R₁₈ has an ionic and hydrophilic group as asubstituent.),

a β-substituted compound is not less than 60% and an a-substitutedcompound is not more than 40%.

21. A mixture of colorants represented by the following general Formula(10):

{wherein R₂′, R₃′, R₆′, R₇′, R₁₀′, R₁₁′, R₁₄′ and R₁₅′ eachindependently represent an unsubstituted sulfamoyl group (—SO₂NH₂), asulfone group (—SO₃M′) or a hydrogen atom, provided that at least one ofR₂′, R₃′, R₆′, R₇′, R₁₀′, R₁₁′, R₁₄′ and R₁₅′ is an unsubstitutedsulfamoyl group; R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ and R₁₆ represent hydrogenatoms; and M represents a proton, an alkaline metal ion, an alkalineearth metal ion and an onium ion of an organic amine or ammonium ion.}

22. A mixture of colorants obtained by subjecting 4-sulfophthalic acidderivatives to reaction with themselves, or with a phthalic acid(phthalic anhydride) derivative in the presence of a copper compound,followed by subjecting thus obtained compound or a salt thereof toreaction with a chlorinating reagent to convert a sulfonic acid group toa chlorosulfonyl group and subsequent reaction with an amidatingreagent.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail hereinbelow. Acolorant of the present invention represented by the above Formula (1)is obtained by subjecting 4-sulfophthalic acid derivatives to reactionthemselves or subjecting a 4-sulfophthalic acid derivative to reactionwith a phthalic acid (phthalic anhydride) derivative in the presence ofa copper compound, followed by reaction of thus obtained compound with achlorinating reagent to convert a sulfonic acid group to achlorosulfonyl group, and further reaction with an amidating reagent,and thereby introduccing a sulfonic acid group and an sulfamoyl group ata specific substitution position (β-position) of a phthalocyanine ring.A printed material using said colorant shows very superior ozone gasfastness.

In general, a phthalocyanine derivative may contain substitutionposition isomers of substituents R₁ to R₁₆ in Formula (1) as shownbelow, that are formed inevitably in synthesizing thereof and thesesubstitution position isomers are often regarded as the same derivativeswithout being distinguished each other:

(In Formula (1), M and R₁ to R₁₆ represent each the same meaning as theabove). For the sake of convenience in the present description, threekinds of phthalocyanine derivatives having a different substitutionposition are classified as defined below into (1) a substitution type atthe β-position, (2) an substitution type at the a-position and (3) amixed substitution type at a- and β-positions, which are used inexplaining phthalocyanine derivatives having different substitutionpositions.

In the following explanation, the 1st to the 16th substitution positionsrepresent the position on a benzene ring to which substituent of R₁ toR₁₆ is bonded, respectively, which should be similar hereinbelow in thepresent description.

(1) a substitution type at the β-position: a phthalocyanine coloranthaving a specific substituent at the 2nd and/or 3rd, 6th and/or 7th,10th and/or 11th, and 14th and/or 15th positions.

(2) a substitution type at the a-position: a phthalocyanine coloranthaving a specific substituent at the 1st and/or 4th, 5th and/or 8th, 9thand/or 12th, and 13th and/or 16th positions.

(3) a mixed substitution type at the a- and β-positions: aphthalocyanine colorant having a specific substituent at an optionalposition among the 1st to 16th positions.

Whether the above phthalocyanine colorant is a substitution type at theβ-position or a substitution type at the a-position substitution type ora mixed substitution type at the a- and β-positions can be identified bydecomposing it to a phthalic acid derivative using nitric acid, and thelike, and examining the substitution position using NMR.

That is, decomposition of a phthalocyanine colorant of a substitutiontype at the β-position provides a phthalic acid derivative substitutedat 4^(th)-position, decomposition of a phthalocyanine colorant of asubstitution type at the a-position provides a phthalic acid derivativesubstituted at 3^(rd)-position, and decomposition of a phthalocyaninecolorant of a mixed substitution type at the a- and β-positions providesa phthalic acid derivative substituted at 3^(rd) and 4^(th)-positions,respectively.

In the above Formula (1), M represents a hydrogen atom, a metal atom, ametal oxide, a metal hydroxide or a metal halide. A metal atom includesspecifically, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W,Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga,In, Si, Ge, Sn, Pb, Sb, and Bi. A metal oxide includes such as VO andGeO. A metal hydroxide includes, for example, Si(OH)₂, Cr(OH)₂, Sn(OH)₂and AlOH. A metal halide includes, for example, SiCl₂, VCl, VCl₂, VOC,FeCl, GaCl, ZrCl and AlCl. Among these, Cu, Ni, Zn, Al and AlOH arepreferable and Cu is most preferable.

Unless otherwise stated in the present description, the number of carbonatoms is not limited especially in an alkyl group, an alkoxyl group, analkenyl group and a cycloalkyl group, and the like, as long as theobject of the present invention can be attained. The approximate numberof carbon atoms in these groups is usually 1 to 16, preferably 1 to 12,more preferably 1 to 6 and still more preferably 1 to 4. However, it isusually 3 to 12, preferably about to 8 as for a cycloalkyl group. Thekind of a substituent, if contained in these groups, is not limitedespecially as long as the object of the present invention can beattained. A preferable substituent on the carbon chain of these groupsincludes, for example, a sulfonic acid group and a group derivedtherefrom (a sulfoneamide group, etc.), a carboxyl group and a groupderived therefrom (a carboxylate ester group, etc.), a phosphono groupand a group derived therefrom (a phosphate ester group, etc.), ahydroxyl group, a substituted or unsubstituted alkoxyl group, asubstituted or unsubstituted amino group, a substituted or unsubstitutedaryl group, a halogen atom and a cyano group.

The kind of an aryl group is not limited especially as long as theobject of the present invention can be attained. A phenyl group or anaphthyl group is usually used. A preferable substituent on an arylgroup includes, for example, a substituent mentioned as a preferablesubstituent on the above carbon chain, and a ureido group, a nitro groupand a heterocyclic group.

In the above Formula (3), R₁₇ and R₁₈ represent each independently ahydrogen atom, a substituted or unsubstituted alkyl group, a substitutedor unsubstituted cycloalkyl group, a substituted or unsubstituted arylgroup, a substituted or unsubstituted heterocyclic group and asubstituted or unsubstituted alkenyl group and R₁₇ and R₁₈ may form aring by bonding together, provided that except when both R₁₇ and R₁₈ area hydrogen atom. At least one of R₁₇ and R₁₈ has an ionic andhydrophilic group as a substituent. As the ionic and hydrophilic group,an anionic and hydrophilic group is preferable, including such as asulfonic acid group, a carboxyl group and a phosphono group. These ionicand hydrophilic groups may be a free form or an alkali metal salt, analkaline-earth metal salt, or an onium ion salt of an organic amine oran ammonium salt. The alkali metal includes, for example, sodium,potassium and lithium. The alkaline-earth metal includes, for example,calcium and magnesium. The organic amine includes, for example, analkylamine such as a lower alkylamine of 1 to 4 carbon atoms includingmethylamine and ethylamine. An alkanolamine includes, for example, amono-, di- or tri-(lower alkanolamine of 1 to 4 carbon atoms) such asmonoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine,diisopropanolamine and triisopropanolamine. The preferable salt includesa salt of ammonium, sodium, potassium, lithium, monoethanolamine,diethanolamine, triethanolamine, monoisopropanolamine,diisopropanolamine and triisopropanolamine.

The above substituted or unsubstituted alkyl group includes, forexample, an alkyl group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphono group, a hydroxyl group, an alkoxyl group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphono groupand a hydroxyl group are preferable.

The above substituted or unsubstituted cycloalkyl group includes, forexample, a cycloalkyl group of 3 to 12 carbon atoms, preferably acycloalkyl group of 5 to 8 carbon atoms. A substituent on saidcycloalkyl ring includes, for example, a sulfonic acid group, a carboxylgroup, a phosphono group, a hydroxyl group, an alkoxyl group, an aminogroup (which may be substituted with an alkyl group, an aryl group andan acetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphono groupand a hydroxyl group are preferable.

Number of carbon atoms of an alkyl group in the above the alkyl groupsubstituted with an aryl group (an aralkyl group) is preferably about 1to 12. Said aralkyl group may have a substituent and example of saidsubstituent includes, for example, a sulfonic acid group, a carboxylgroup, a phosphono group, a hydroxyl group, an amino group (which may besubstituted with an alkyl group, an aryl group and an acetyl group), aureido group, an alkyl group, an alkoxyl group, a nitro group, a cyanogroup, a heterocyclic group and a halogen atom. Among these groups, asulfonic acid group, a carboxyl group, a phosphono group and a hydroxylgroup are preferable.

The above substituted or unsubstituted aryl group includes, for example,a phenyl group and a naphthyl group. The substituent includes, forexample, a sulfonic acid group, a carboxyl group, a phosphono group, ahydroxyl group, an amino group (which may be substituted with an alkylgroup, an aryl group and an acetyl group), a ureido group, an alkylgroup, an alkoxyl group, a nitro group, a cyano group, a heterocyclicgroup and a halogen atom. Among these groups, a sulfonic acid group, acarboxyl group, a phosphono group and a hydroxyl group are preferable.

The above substituted or unsubstituted heterocyclic group is preferablya five-membered or six-membered ring, which may further be a fused ringand may be an aromatic heterocycle or a nonaromatic heterocycle. Theheterocycle includes, for example, pyridine, pyrazine, pyrimidine,pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline,phthalazine, quinoxaline, pyrrol, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline. Theseheterocycles may have a substituent, which includes, for example, asulfonic acid group, a carboxyl group, a phosphono group, a hydroxylgroup, an amino group (which may be substituted with an alkyl group, anaryl group and an acetyl group), a ureido group, an alkyl group, analkoxyl group, a nitro group, a cyano group and a halogen atom.

The above substituted or unsubstituted alkenyl group includes, forexample, an alkenyl group of 1 to 12 carbon atoms. The substituentincludes, for example, a sulfonic acid group, a carboxyl group, aphosphono group, a hydroxyl group, an alkoxyl group, an amino group(which may be substituted with an alkyl group, an aryl group and anacetyl group), an aryl group, a halogen atom and a cyano group. Amongthese groups, a sulfonic acid group, a carboxyl group, a phosphono groupand a hydroxyl group are preferable.

In Formula (1), R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅ each independentlyrepresent an unsubstituted sulfamoyl group represented by Formula (2), asubstituted sulfamoyl group represented by Formula (3), or a hydrogenatom, provided that at least one of R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ andR₁₅ is the unsubstituted sulfamoyl group, and at least one thereof isthe substituted sulfamoyl group; and R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ andR₁₆ represent hydrogen atoms; the sum of a number of an unsubstitutedsulfamoyl group and a number of a substituted sulfamoyl group is 2 to 4,and a number of an unsubstituted sulfamoyl group is 1 to 3 and a numberof a substituted sulfamoyl group is 1 to 3.

In each of combinations of R₂ and R₃, R₆ and R₇, R₁₀ and R₁₁, and R₁₄and R₁₅, preferably one member of each combination is a hydrogen atom,and the other is an unsubstituted sulfamoyl group (—SO₂NH₂) or asubstituted sulfamoyl group represented by Formula (3), and among R₂,R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅, at least one is an unsubstitutedsulfamoyl group and at least one is a substituted sulfamoyl grouprepresented by the above Formula (3).

Specific combination examples of a metal (M) and a compound representedby the above Formula (3) in the phthalocyanine compounds represented bythe above Formula (1) of the present invention are shown in Tables 1 to5, but the phthalocyanine compounds used in the present invention arenot limited to the following examples. In the Tables, a compoundrepresented by the above Formula (3) is shown in a free acid form. No. M

1 Cu

2 Cu

3 Cu

4 Cu

5 Cu

6 Cu

7 Cu

8 Cu

9 Cu

10 Cu

11 Cu

12 Cu

13 Cu

14 Cu

15 Cu

16 Cu

17 Cu

18 Cu

19 Cu

20 Cu

21 Cu

22 Cu

23 Cu

24 Cu

25 Cu

26 Cu

27 Cu

28 Cu

29 Cu

30 Cu

31 Cu

32 Cu

33 Cu

34 Cu

35 Cu

36 Cu

37 Cu

38 Cu

39 Cu

40 Cu

41 Cu

42 Cu

43 Cu

44 Cu

45 Cu

46 Cu

47 Ni

48 Ni

49 Ni

50 AlOH

51 AlOH

52 AlOH

53 Zn

54 Zn

55 Zn

A phthalocyanine colorant of the present invention is obtained bysubjecting 4-sulfophthalic acid derivatives to reaction with themselvesor subjecting a 4-sulfophthalic acid derivative to reaction with aphthalic acid (phthalic anhydride) derivative in the presence of ametallo compound to obtain a compound (sulfophthalocyanine of aβ-position substitution type), followed by reaction of this product witha chlorinating reagent to convert a sulfonic acid group to achlorosulfonyl group and further reaction with an amidating reagent andan organic amine. 4-Sulfophthalic acid derivative used as a raw materialusually contains, as impurities, about 15 to 25% by weight of compoundssulfonated in the 3-position and thus compounds substituted at thea-position, derived from such compounds, are mixed in an objectivephthalocyanine colorant. To further enhance effects of the presentinvention (particularly to obtain an ink with higher ozone fastness), itis preferable to use a raw material containing less impuritiessulfonated at the 3-position.

Also in an objective phthalocyanine colorant, compounds formed bydecomposition of a part of chlorosulfonyl groups during the reaction aremixed in the reaction product, however, they are not particularly anobstacle. Thus obtained colorant is represented by Formula (9) as shownbelow and will contain a derivative substituted at the β-position, as amain component, of at least not less than 60%, preferably not less than70% and more preferably not less than 75%:

(In Formula (9), M, R₁₇ and R₁₈ represent each the same meaning asdefined above; l includes 0 and is less than 1, preferably not more than0.7, more preferably not more than 0.5 and most preferably not more than0.3; n is not less than 0.3 and preferably not less than 0.7 and notmore than 3; m is not less than 1 and not more than 3.7; and the totalof l, m and n is not less than 2 and not more than 4; and the values ofl, m and n show each an average value in a mixture.)

In producing a phthalocyanine colorant of the present invention, it ispreferable to adopt ratio (mole ratio) of an amidating reagent to anorganic amine corresponding to a substituted sulfamoyl group representedby Formula (3) such that ratio of an unsubstituted sulfamoyl group to asubstituted sulfamoyl group in said phthalocyanine colorant falls in therange of 1:3 to 3:1. High ratio of an unsubstituted sulfamoyl group(high reaction ratio of an amidating reagent) gives high ozone fastnessof a recorded image by an ink containing thus obtained phthalocyaninecolorant, while the colorant tends to have low water-solubility andcause bronze phenomenon. In contrast, high ratio of an organic aminegives high water-solubility of thus obtained phthalocyanine colorant,causing little bronze phenomenon, while low ozone fastness of an image.Therefore, in response to the kind of an organic amine to be used, ratioof the amidating reagent and the organic amine can be adjusted, asappropriate, to obtain good balance.

A method for producing a compound of the present invention representedby Formula (1) will be described.

At first, a metallo phthalocyanine sulfonic acid represented by theabove Formula (5) is synthesized. As described above, a compoundsubstituted at the a-position, derived from raw materials is formed as abyproduct in the production of a phthalocyanine colorant of the presentinvention, but the production method is described here in reference to acompound substituted at the β-position, that is, a main component.

A metallo phthalocyanine sulfonic acid represented by Formula (5) can besynthesized, for example, by subjecting 4-sulfophthalic acid derivativesto reacting with themselves or subjecting a 4-sulfophthalic acidderivative to reaction with a phthalic acid (phthalic anhydride)derivative in the presence of, for example, a catalyst and a metallocompound.

By changing reaction mol ratio of a 4-sulfophthalic acid derivative to aphthalic acid (phthalic anhydride) derivative, the number of sulfonegroups, that is, values of a to d can be adjusted. The 4-sulfophthalicacid derivative includes 4-sulfophthalic acid, 4-sulfophthalicanhydride, 4-sulfophthalimide, 4-sulfophthalonitrile, 4- or5-sulfo-2-cyanobenzamide, 5-sulfo-1,3-diiminoisoindolin or saltsthereof. Among these compounds, 4-sulfophthalic acid or a salt thereofis usually preferable. When phthalic acid, phthalic anhydride andphthalimide are used, the addition of urea is essential. Use amount ofthe urea is 5 to 100 times mol based on 1 mol of a 4-sulfophthalic acidderivative.

{In Formula (5), M, L, a, b, c and d represent each the same meaning asabove.}

The reaction is usually carried out in the presence of a solvent. Anorganic solvent with boiling point not lower than 100° C., preferablynot lower than 130° C. is used as the solvent, which includes, forexample, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol,1-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol,propylene glycol, trichlorobenzene, chloronaphthalene, nitrobenzene,quinoline, sulfolane and urea. Use amount of the solvent is 1 to 100times by mass of that of a 4-sulfophthalic acid derivative.

The catalyst includes 1,8-diazabicyclo[5,4,0]-7-undecene, ammoniummolybdate and boric acid. Amount of the addition is 0.001 to 1 mol basedon 1 mol of a 4-sulfophthalic acid derivative.

The metallo compound includes a halide, a carboxylate, a sulfate, anitrate, an acetylacetonate, a carbonyl compound, a complex, and thelike of such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co,Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge,Sn, Pb, Sb and Bi. For example, copper chloride, copper bromide, nickelchloride, nickel acetate, cobalt chloride, cobalt acetate and cobaltacetylacetonate are included. Use amount of the metallo compound is 0.15to 0.35 times mol based on 1 total mol of 4-sulfophthalic acidderivatives or 1 total mole of a 4-sulfophthalic acia derivative and an(unsubstituted) phthalic acid derivative.

Reaction temperature is usually 100 to 290° C. and preferably 130 to270° C. Reaction time depends on reaction temperature, but is usually 1to 8 hours. Metallo Phthalocyanine tetrasulfonic acid or a salt formthereof is obtained by filtration, salting out (or acid depositing) anddrying after completion of the reaction. When a free acid is desired,for example, the reaction product is deposited using an acid. When asalt is desired, the reaction product is salted out, but when a desiredsalt is not obtained by salting out, for example, an ordinary method forsalt exchanging, where a free acid is added with a desired organic orinorganic base can be used.

Copper phthalocyanine sulfonic acid or a salt thereof in the aboveFormula (6), where M is copper, is synthesized by a method described inPatent Literature 8. Copper phthalocyanine tetrasulfonic acid in theabove Formula (6), where a, b, c and d are each 1, is obtained byreacting 4-sulfophthalic acid (1 mol), copper chloride (II) (0.3 mol),ammonium phosphomolybdate (0.003 mol), urea (6 mol) and ammoniumchloride (0.5 mol) at 180° C. for 6 hours in a sulfolane solvent.However, as reactivity depends on the kinds and use amount of a4-sulfophthalic acid derivative, a metallo compound, a solvent, acatalyst, and the like, these reaction conditions are not limited to theabove.

By subjecting phthalocyanine sulfonic acid or a salt thereof representedby Formula (5) to reaction with a chlorinating reagent in a solvent suchas an organic solvent, sulfuric acid, fuming sulfuric acid orchlorosulfonic acid, metallophthalocyanine sulfonic chloride representedby Formula (7) is obtained. The chlorinating reagent is preferably usein excess to a sulfonic acid group of phthalocyanine sulfonic acid or asalt thereof, and is about 1 to 10 times, preferably not less than 1.5times, as mole ratio to the sulfonic acid group. The organic solvent tobe used in the reaction includes, but is not limited to, such asbenzene, toluene, nitrobenzene, chlorobenzene, N,N-dimethylformamide andN,N-dimethylacetoamide. The chlorinating reagent includes, but is notlimited to, such as chlorosulfonic acid, thionyl chloride, sulfurylchloride, phosphorus trichloride, phosphorus pentachloride andphosphorus oxychloride. With regard to a phthalocyanine colorant of thepresent invention, impurities may be formed by chlorination of aphthalocyanine nucleus and mixed in the reaction product.

(wherein M, a, b, c and d represent each the same meaning as above.)

Thus obtained phthalocyanine tetrasulfonic chloride is then reacted witha corresponding organic amine and an amidating reagent in water solventusually at pH 6 to 10, usually at 5 to 70° C. and usually for 1 to 20hours to obtain an objective compound. The total use amount (mole ratio)of the amidating reagent and the above organic amine is preferably notless than the equimolar ratio to the sulfonic chloride group of theabove phthalocyanine sulfonic chloride, usually 1 to 20 times by moleand preferably 1.5 to 5 times by mole. The use ratio of the aboveorganic amine may be decided according to the ratio of substitutedsulfamoyl groups of the objective compound.

An amidating reagent to be used in the reaction includes, but is notlimited to, for example, an ammonium salt such as ammonium chloride andammonium sulfate; urea, ammonia water and ammonia gas.

Use amount of the organic amine is usually not less than one mole timeof the theoretical value based on 1 mol of a phthalcyanine compound. Theamount depends on reactivity of the organic amine and reactionconditions and is not limited to the above amount.

With regard to a phthalocyanine colorant of the present invention, adimer (for example, Pc-L-Pc) or a trimer of a phthalocyanine ring (Pc)linked through a divalent bonding group (L) may be partially formed andmixed in the reaction product as impurities, wherein (L) present inmultiple may be same or different.

The divalent bonding group represented by L includes a sulfonyl group(—SO₂—) and —SO₂—NH—SO₂— and the like. The bonding group may also be agroup formed by combining these groups.

Thus obtained phthalocyanine colorant of the present invention can beseparated by filtration, and the like, after precipitating with acid orsalting out. Salting out is preferably carried out in, for example,acidic to alkaline conditions, preferably in a range of pH 1 to 11.Temperature in salting out is not limited especially, however, saltingout is preferably carried out by adding sodium chloride, and the likeafter heating usually at 40 to 80° C., preferably 50 to 70° C.

A phthalocyanine colorant of the present invention that is synthesizedby the above method and represented by the above Formula (1) is obtainedin a form of a free acid or a salt thereof. When a free acid is desired,the reaction product is precipitated using an acid. When a salt isdesired, the reaction product is salted out, but when a desired salt isnot obtained by salting out, for example, an ordinary method for saltexchanging, where a desired organic or inorganic base is added to a freeacid of a compound, can be used.

A cyan ink of the present invention contains a phthalocyanine colorantof the above Formula (1) produced by the above method and is preparedusing water as a medium, and when the ink is used as an ink for ink-jetrecording, the phthalocyanine colorant with lower content of an anionsuch as Cl⁻ and SO₄ ²⁻ is preferable, and general standard of the totalcontent of Cl⁻ and SO₄ ²⁻ is not higher than 5% by weight, preferablynot higher than 3% by weight and more preferably not higher than 1% byweight in the phthalocyanine colorant, while not higher than 1% byweight in the ink. To produce a phthalocyanine colorant of the presentinvention having lower Cl⁻ and SO₄ ²⁻, a method for desalting can beapplied using, for example, an ordinary method using a reverse osmosismembrane or a method for subjecting a dried solid or a wet cake of aphthalocyanine colorant of the present invention to stirring in mixedsolvent of an alcohol and water, filtering and drying. An alcohol to beused is a lower alcohol of 1 to 4 carbon atoms, preferably 1 to 3 carbonatoms and more preferably methanol, ethanol or 2-propanol. In desaltingusing an alcohol, a method for desalting by heating the alcohol to nearboiling point thereof and then cooling can also be adopted. The contentof Cl⁻ and SO₄ ⁻ is measured by, for example, an ion chromatography.

In using a cyan ink of the present invention as an ink for ink-jetrecording, it is preferable to use a phthalocyanine colorant having alower content of a heavy metal (ion) such as zinc and iron and a metal(cation) such as calcium and silica (except a metal (M in Formula (1))contained in phthalocyanine skeleton). A general standard content in apurified and dried phthalocyanine colorant is, for example, not higherthan about 500 ppm for each heavy metal (ion) such as zinc and iron anda metal (cation) such as calcium and silica. The content of a heavymetal (ion) and a metal (cation) is measured by an ion chromatography,an atomic absorption analysis or an ICP (Inductively Coupled Plasma)emission analysis.

An ink of the present invention contains 0.1 to 8% by mass, preferably0.3 to 6% by mass of a phthalocyanine colorant of the above Formula (1).An ink of a lower concentration type contains 0.1 to 2.5% by weight of aphthalocyanine compound of the present invention.

An ink of the present invention is prepared using water as a medium. Anink of the present invention contains 0.3 to 6% by mass of a mixture ofa compound of the above Formula (1) obtained as above and has the aboveconditions or a salt thereof. An ink of the present invention furthercontains a water-soluble organic solvent, as needed, within the contentrange not impairing the effect of the present invention. A water-solubleorganic solvent is used as a dye-dissolving agent, an agent forprohibiting dryness (a wetting agent), a viscosity modifier, apenetration promoter, a surface tension modifier, an antifoaming agent,and the like. Other ink modifiers include known additives such as anantiseptics-and-fungicide, a pH controller, a chelate agent, a rustprventive, an ultraviolet absorber, a viscosity modifier, adye-dissolving agent, a fading inhibitor, an emulsion stabilizer, asurface tension modifier, an antifoaming agent, a dispersing agent and adispersion stabilizer. Content of a water-soluble organic solvent is 0to 60% by mass, preferably 10 to 50% by mass based on the total amountof an ink and an ink modifier is preferably used in 0 to 20% by mass,preferably 0 to 15% by mass based on the total amount of an ink. Theremainder other than the above is water.

A water-soluble organic solvent that can be used in the presentinvention includes, for example, C₁₋₄ alkanols such as methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol andtert-butanol; carboxamides such as N,N-dimethyl formamide andN,N-dimethyl acetamide; heterocyclic ketones such as 2-pyrrolidone,N-methyl-2-pyrrolidone, 1,3-dimethyimidazolidin-2-one and1,3-dimethylhexahydropyrimid-2-one; ketones or keto-alocohols such asacetone, methyl ethyl ketone and 2-methyl-2-hydroxypentane-4-one; cyclicethers such as tetrahydrofuran and dioxane; monomers or oligomers orpolyalkylene glycols or thioglycols having (C₂₋₆) alkylene unit such asethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butyleneglycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethyleneglycol and polypropylene glycol; polyol(triol) such as glycerine andhexane-1,2,6-triol; (C₁₋₄) alkyl ethers of polyhydric alcohols such asethylene glycol monomethyl ether, ethylene glycol monoethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,triethylene glycol monomethyl ether and triethylene glycol monoethylether; γ-butyrolactone and dimethylsulfoxide.

In an ink according to the present invention, a preferable water-solubleorganic solvent includes a mono- or polyhydric alcohol having carbonatoms of 3 to 8, and 2-pyrrolidone which may have a substituent of analkyl group having carbon atoms of 1 to 3, and the like, and as apolyhydric alcohol, one having 2 to 3 hydroxyl groups is preferable.Typically, isopropanol, glycerine, mono, di- or triethylene glycol,dipropylene glycol, 2-pyrrolidone and N-methyl-2-pyrrolidone, butanol,and the like are included and isopropanol, glycerine, diethylene glycoland 2-pyrrolidone are more preferable. These water-soluble organicsolvents are used alone or in combination.

An antiseptics and fungicide include organosulfur type, organonitrogensulfur type, organohalogen type, haloarylsulfone type, iodopropargyltype, N-haloalkylthio type, benzothiazole type, nitrile type, pyridinetype, 8-hydroxyquinoline, isothiazoline type, dithiol type, pyridineoxide type, nitropropane type, organotin type, phenol type, quaternaryammonium salt type, triazine type, thiadiazine type, anilide type,adamantane type, dithiocarbamate type, brominated indanone type,benzylbromacetate type, inorganic salts, etc. An organohalo typecompounds include, for example, sodium pentachlorophenolate, andpyridine oxide type compounds include, for example,2-pyridinethiol-1-oxide sodium salt, and inorganic salt type compoundsinclude, for example, anhydrous sodium acetate, and isothiazoline typecompounds include, for example, 1,2-benzisothiazoline-3-one,2-n-octyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazoline-3-one,5-chloro-2-methyl-4-isothiazoline-3-one magnesium chloride,5-chloro-2-methyl-4-isothiazoline-3-one calcium chloride and2-methyl-4-isothiazoline-3-one calcium chloride, and the like. Otherantiseptics and fungicide includes sodium sorbate, sodium benzoate, andthe like (for example, Proxcel GXL(S) (trade name)) and Proxcel XL-2(S)(trade name), and the like manufactured by Abesia Co., Ltd.).

As for a pH adjustor, any substance can be used as far as it can controlpH of an ink within the range of 6.0 to 11.0 to improve storagestability of an ink. For example, alkanolamines such as diethanolamineand triethanolamine; alkali metal hydroxides such as lithium hydroxide,sodium hydroxide and potassium hydroxide; ammonium hydroxide; and alkalimetal carbonates such as lithium carbonate, sodium carbonate andpotassium carbonate are included.

Chelate agents include, for example, sodium ethylendiaminetetraacetate,sodium nitrilotriacetate, hydroxyethyl sodium ethylenediaminetriacetate, sodium diethylenetriamine pentaacetate, uramil sodiumdiacetate, etc. Rust preventives include, for example, acidic sulfite,sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite,pentaerithritol tetranitrate, dicyclohexylammonium nitrite, etc.

An ultraviolet absorber, for example, a benzophenone type compound, abenzotriazole type compound, a cinnamic acid type compound, a triazinetype compound, a stilbene type compound, or a compound which emitsfluorescence by absorbing ultraviolet rays, represented by a benzoxazoletype compound, a so-called fluorescent brightening agent can also beused.

As a viscosity modifier, a water soluble polymer compound isexemplified, for example, polyvinyl alcohol, cellulose derivatives,polyamine, polyimine, and the like, besides a water soluble organicsolvent.

A dye solubilizer includes, for example, urea, e-caprolactam, ethylenecarbonate, and the like.

A fading inhibitor is used to improve image storage ability. As thefading inhibitor, various kinds of an organic-series or a metalcomplex-series fading inhibitor can be used. Organic fading inhibitorsinclude, for example, hydroquinones, alkoxyphenols, dialkoxyphenols,phenols, anilines, amines, indanes, chromans, alkoxyanilines andheterocycles. Metal complexes include nickel complex, zinc complex, etc.

A surface tension modifier includes surfactants such as anionicsurfactants, amphoteric surfactants, cationic surfactants and nonionicsurfactants. Anionic surfactants include salts such asalkylsulfocarboxylate, a-olefinsulfonate, polyoxyethylenealkyletheracetate, N-acylamino acids and salts thereof, N-acylmethyltaurine salts,alkylsulfate polyoxyalkylethersulfate, alkylsulfatepolyoxyethylenealkyletherphosphate, rosin acid soap, castor oil sulfate,lauryl alcohol sulfate, alkylphenol phosphate, alkyl phosphate,alkylaryl sulfonate, diethyl sulfosuccinate, diethylhexylsulfosuccinate, dioctyl sulfosuccinate; cationic surfactants include2-vinylpyridine derivatives and poly(4-vinylpyridine) derivatives.Amphoteric surfactants include lauryldimethylaminoacetic acid betaine,2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, palm oilfatty acid amide propyl dimethylamino acetic acid betaine,polyoctylpolyaminoethyl glycine and other imidazolidine derivatives.Nonionic surfactants include ethers such as polyoxyethylene nonylphenylether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenylether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether,polyoxyethylene alkyl-ethers and polyoxy aryl alkyl ether;polyoxyethylene oleic acid; esters such as polyoxyethylene oleate,polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate,sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleateand polyoxyethylene stearate; acetylene glycols such as2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,6-dimethyl-4-octyn-3,6-diol and3,5-dimethyl-1-hexyn-3-ol (for example, Surfinol-104, -104PG50, -82,-465, Olfin-STG, manufactured by Nisshin Chem. Co., Ltd.). These inkmodifiers are used alone or in combination. In this connection, surfacetension of an ink according to the present invention is usually 25 to 70mN/m, more preferably 25 to 60 mN/m. And viscosity of an ink accordingto the present invention is preferably not higher than 30 mPa·s.Further, it is more preferable to adjust it to not higher than 20 mPa·s.

As an antifoaming agent, a fluorine-based or a silicone-based compoundis used, if necessary.

On producing an ink according to the present invention, order ofdissolving each agent is not limited in particular. In preparation of anink, water used is preferably such one as contains low impurities, suchas ion-exchanged water or distilled water. Further, foreign matters maybe removed by micro-filtration with a membrane filter, and the like, ifnecessary, and in case of using it as an ink for an ink-jet printer,conducting micro-filtration is preferable. A pore diameter inmicro-filtration is usually 1 micrometer to 0.1 micrometer, preferably0.8 micrometer to 0.2 micrometer.

An ink according to the present invention can be used not only formonochrome image formation, but also for full-colored image formation.For full-colored image formation, it is also used as an ink set togetherwith a magenta ink, yellow ink, and black ink. Further, to form an imagewith high resolution, it is also used as an ink set together with alight magenta ink, blue ink, green ink, orange ink, dark yellow ink,grey ink, and the like.

As a colorant applicable to a yellow ink, various types can be used. Forexample, it includes aryl or heterylazo dyes having phenols, naphthols,anilines, heterocyclics such as pyrazolone and pyridone, and open chaintype active methylene compounds as a coupling component (hereinaftercalled as a coupler component); azomethine dyes having open chain typeactive methylene compounds as a coupler component; methine dyes such asbenzylidene dyes, monomethine oxonol dyes, and the like; quinone typedyes such as naphthoquinone dyes, anthraquinone dyes, and the like; andas other types of dyes, quinophthalone dyes, nitro-nitroso dyes,acridine dyes, acridinon dyes, and the like.

As a colorant applicable to a magenta ink, various types can be used.For example, it includes arylazo dyes having phenols, naphthols,anilines as a coupler component; azomethine dyes having pyrazolones andpyrazolotriazoles as a coupler component; methine dyes such as arylidenedyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes, and thelike; carbonium dyes such as diphenylmethane dyes, triphenylmethanedyes, and xanthene dyes; quinone dyes such as naphthoquinone dyes,anthraquinone dyes, and anthrapyridone dyes; and fused polycyclic dyessuch as dioxazine dyes; and the like.

Each colorant described above may exhibit each color of yellow, magentaand cyan for the first time after a part of chromophores is dissociated,and in that case, a counter cation may be an inorganic cation of such asan alkali metal or ammonium, or an organic cation such as pyridinium anda tertiary ammonium salt, and further a polymer cation which has theseas partial structure thereof. As a black colorant applicable, adispersion of carbon black can be exemplified besides disazo, trisazoand tetraazo dyes.

An ink according to the present invention can be used in a recordingmethod such as in printing, duplication, marking, writing, drafting,stamping, and the like, and particularly is suitable for use in ink-jetprinting.

An ink-jet recording method according to the present invention affordsenergy to an ink prepared as described above, and form an image on knownimage receiving materials, namely a plain paper, a resin-coated paper, aprofessional paper for an ink-jet, a glossy paper, a glossy film, apaper commonly used for electronic photography, a fiber or a cloth(cellulose, nylon, wool, and the like), glass, metal, pottery, leather,and the like.

On forming an image, to furnish gloss or water fastness, or to improveweather fastness, dispersion of polymer particulates (also said aspolymer latex) may be used together. As for a period during whichpolymer latex is furnished to a recording material, it may be before,after, or at the same time of providing a colorant, and accordingly alsoa place of the addition thereof may be in a recording material, or in anink, or it may be used as a liquid material of a polymer latex alone.

Hereinafter is explained, a recording material (especially, recordingpaper and a recording film) used for ink-jet printing sing an inkaccording to the present invention. A backing material in a recordingpaper and a recording film consists of a chemical pulp such as LBKP,NBKP, and the like; a mechanical pulp such as GP, PGW, RMP, TMP, CTMP,CMP, CGP, and the like; a waste paper pulp such as DIP, and the like;and those produced using various types of apparatus such as Fourdriniermachine, cylinder paper machine, and the like after mixing additives, ifnecessary, such as a pigment, a binder, a sizing agent, a fasteningagent, a cationic agent, a strengthening agent for paper, and the like,can be used. In addition to these backing materials, a synthetic paperand a plastic film and sheet may be used, and thickness of the backingmaterial is preferably 10 to 250 μm, and basis weight is desirably 10 to250 g/m². The backing material may be provided with an ink receivinglayer and a back coating layer as it is, or may be provided with an inkreceiving layer and a back coating layer after it is provided with asize press or an anchor coat layer with starch or polyvinyl alcohol.Further, the backing material may be subjected to treatment forsmoothing with a calendering device such as a machine calender, a TGcalender, a soft calender, and the like. In the present invention, as abacking material, a paper laminated with a polyolefin (for example,polyethylene, polystyrene, polyethylene terephthalate, polybutene, and acopolymer thereof) at both surfaces and a plastic film are preferablyused. Into a polyolefin, white pigments (for example, titanium oxide,zinc oxide) or toning dyes (for example, cobalt blue, ultramarine blue,neodymium oxide) are preferably added.

In the ink receiving layer provided on the carrier, a pigment or awater-based binder may be contained. As the pigment, a white pigment ispreferable, including a white inorganic pigment such as calciumcarbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphoussilica, aluminum silicate, magnesium silicate, calcium silicate,aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calciumsulfate, titanium dioxide, zinc sulfide, zinc carbonate, and the like;and an organic pigment such as a styrene rubber based pigment, anacrylic resin based pigment, a urea resin, a melamine resin, and thelike. As a white pigment contained in the ink receiving layer, a porousinorganic pigment is preferable, in particular, synthetic amorphoussilica having large pore area, and the like are suitable. As thesynthetic amorphous silica, a silicic anhydride obtained by a dryproduction method, and a water-containing silicic acid obtained by a wetproduction method, can be used, and it is particularly desirable to usea water-containing silicic acid.

As the water-based binder contained in the ink receiving layer, awater-soluble polymer such as polyvinyl alcohol, silanol modifiedpolyvinyl alcohol, starch, cation type starch, casein, gelatin,carboxylmethyl cellulose, hydroxylethyl cellulose, polyvinylpyrrolidone, a polyalkylene oxide, derivatives of a polyalkylene oxide,and the like, and a water-dispersible polymer such as styrene-butadienerubber latex, acrylic resin based emulsion, and the like, areexemplified. These water-based binders can be used alone or incombination with at least two kinds thereof. In the present invention,among these, especially polyvinyl alcohol and silanol modified polyvinylalcohol are suitable from the points of adhesion property to a pigment,and resistance to peeling-off of an ink receiving layer. The inkreceiving layer can contain, besides a pigment and a water-based bondingagent, a mordant, a water fastness modifier, a light fastness improver,a surfactant, and other additives.

As a mordant added in an ink receiving layer, for example, a polymermordant is used.

A water fastness modifier is effective for modifying water fastness ofan image, and as the water fastness modifier, a cationic resin isdesirable, in particular. Such a cationic resin includes polyamidepolyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, apolymer of dimethyl diallyl ammonium chloride, cationic polyacrylamide,a colloidal silica, and the like, and among these cationic resins,particularly polyamide polyamine epichlorohydrin is suitable. Content ofthese cationic resins is preferably 1 to 15% by weight, particularlypreferably 3 to 10% by weight, based on the total solid portion in anink receiving layer.

The light fastness improver includes zinc sulfate, zinc oxide, ahindered amine type antioxidant, an ultra violet light absorber such asa benzophenone type and a benzotriazole type absorber, and the like.Among these, zinc sulfate is suitable.

A surfactant functions as a coating coagent, a peel improver, a slideimprover, or an antistatic agent. Instead of a surfactant, an organicfluorocompound may be used. A hydrophobic organic fluorocompound ispreferable. Examples of the organic fluorocompound include afluorine-based surfactant, an oily state fluorine-based compound (forexample, a fluoro-oil), and a solid state fluorocompound resin (forexample, a tetrafluoroethylene resin). As the other additives added inan ink receiving layer, a pigment dispersing agent, a thickener, anantifoaming agent, dyes, a fluorescent whitener, a preservative, a pHadjustor, a matting agent, a hardener, and the like are exemplified. Inthis connection, the ink receiving layer may be one layer or two layers.

On a recording paper and a recording film, a back coating layer may beprovided, and as a component possible to be added in this layer, a whitepigment, a water-based binder, and other components are exemplified.White pigments contained in a backcoat layer includes, for example,white inorganic pigments such as precipitated calcium carbonate, groundcalcium carbonate, kaoline, talc, calcium sulfate, barium sulfate, titandioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminumsilicate, diatomite, calcium silicate, magnesium silicate, syntheticamorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite,aluminum hydroxide, alumina, lithopone, zeolite, hydrated halloysite,magnesium carbonate and magnesium hydroxide; and organic pigments suchas styrenic plastic pigments, acrylic plastic pigments, polyethylene,microcapsule, a urea-resin and a melanin-resin.

A water-based binder contained in a backcoat layer includepoly(styrene-co-maleate salt), poly(styrene-co-acrylate salt);water-soluble polymers such as polyvinyl alcohol, silanol modifiedpolyvinyl alcohol, starch, cationic starch, casein, gelatin,carboxymehthylcellulose, hydroxyehthylcellulose andpolyvinylpyrrolidone; and water dispersible polymers such asstyrene-butadiene latex, acrylic emulsion, etc. The other componentscontained in the back coating layer includes an antifoaming agent, afoam inhibiting agent, dyes, a fluorescent whitener, antiseptics, awater fastness modifier, and the like.

In a composing layer of an ink-jet recording paper and a recording film(containing a back coating layer), polymer latex may be added. Thepolymer latex is used to improve physical properties of a membrane suchas for dimensional stabilization, curling prevention, adhesionprevention, and crazing prevention of a membrane. When polymer latexhaving low glass transition temperature (of not higher than 40° C.) isadded in a layer containing a mordant, crazing or curling of the layercan be prevented. Moreover, when polymer latex having high glasstransition temperature is added in a back coated layer, curling of thelayer can also be prevented.

These recording papers and recording films are generally called as apaper for professional of an ink-jet, a glossy paper or a glossy film,and they are commercially sold, for example, as Pictoriko (trade name:manufactured by Asahi Glass Co. Ltd.), Color BJ Paper, High QualityProfessional Paper, Color BJ Photofilm Sheet, Super Photopaper,Professional Photopaper (all of these are trade names: manufactured byCanon Inc.), Paper for Color Image Jet (trade name: manufactured bySharp Corporation.), Paper for PM Photo, Glossy Film Professional forSuper Fine Use (all of these are trade names: manufactured by Epson Co.,Ltd.), PictaFine (trade name: manufactured by Hitachi Maxell, Ltd.), andthe like. Especially, an ink-jet recording method using an ink accordingto the present invention functions particularly effectively on arecording paper and a recording film having an image receiving layerwith an ink, which layer, as a recording material, contains whiteinorganic pigment particles on a carrier. In this connection, it isnaturally utilizable also to a usual paper.

A colored article according to the present invention is one obtained bycoloring a material to be colored with the above-described ink using anink-jet printer. A material to be colored is not limited in particularas long as it is the above-described recording material or othermaterials possible to be colored with an ink-jet printer.

To record on a recording material by an ink-jet recording methodaccording to the present invention, it is enough to record on arecording material in a usual method, for instance, after setting acontainer containing the above-described ink at a predetermined positionof an ink-jet printer. The ink-jet printer, for example, includes apiezo-type printer utilizing mechanical vibration, a bubble-jet printer(trade mark) utilizing foams generated by heating, and the like.

The ink according to the present invention does not occur precipitationand separation during storage. Furthermore, when the ink according tothe present invention is used in ink-jet printing, a jetting device (anink head) is not clogged. The ink according to the present inventiondoes not cause change in physical properties even under constantrecirculation for a comparatively long period by a continuous ink-jetprinter, or on intermittent use by an on-demand style ink-jet printer.

An ink of the present invention exhibits a clear cyan color when apreferable colorant is used. Moreover, according to the ink, a recordedarticle especially excellent in ozone fastness, light fastness and waterfastness can be obtained. By using it as a set of dark-and-light cyaninks, a recorded article which is further excellent in ozone fastness,light fastness and water fastness can be obtained. Furthermore, by usingit together with other inks such as yellow, magenta and, if necessary,green, red, orange, blue, and the like, color tones of a broad visiblerange can be exhibited, and a recorded article excellent in ozonefastness, and also excellent in light fastness and water fastness can beobtained.

EXAMPLES

The present invention is more specifically explained by Examples asfollows, however, the present invention should not be limited thereto.In this connection, “part” and “%” in the specification are based onweight unless otherwise specified.

Example 1-1

Synthesis of the compound of Formula (1), wherein M is copper, havingtwo unsubstituted sulfamoyl groups and two substituted sulfamoyl groupsof Formula (3) positioned at the β-position, and in Formula (3), R₁₇ isa 2-sulfoethyl group and R₁₈ is a hydrogen atom:

(1) Synthesis of copper phthalocyanine tetrasulfonic acid tetrasodiumsalt (a substitution type at the β-position) (A compound of Formula (5)wherein, M is Cu, all of a, b, c and d are 1, and all of L are Na)

To a four-necked flask provided with a cooling tube, 40 parts ofsulfolane is added, and a temperature thereof was raised to 180° C. inone hour. Therein, 40 parts of a monosodium salt of 4-sulfophthalicacid, 4.5 parts of ammonium chloride, 55 parts of urea, 0.5 parts ofammonium molybdate, and 6 parts of copper (II) chloride were added,stirred at the same temperature for 6 hours. After the reaction solutionwas cooled to 40° C., an objective substance was filtered with Nutsche,and washed with 400 parts of methanol. Subsequently, 300 parts of waterwas added to a wet cake obtained, and pH thereof was adjusted to 11using a 48% aqueous solution of NaOH, and the solution was stirred at80° C. for one hour. A 35% aqueous solution of hydrochloric acid wasadded threto while stirring to make pH thereof 3, then gradually addedthereto 80 parts of sodium chloride. Crystals deposited were filteredand washed with 150 parts of a 20% aqueous solution of sodium chlorideto obtain 90 parts of a wet cake. Then, 210 parts of methanol was addedthereto. After stirring for one hour, thus deposited crystals wereseparated by filtration, washed with 300 parts of a 70% aqueous solutionof methanol and dried to obtain 22.9 parts of copper phthalocyaninetetrasulfonic acid tetra sodium salt of a substitution type at theβ-position, according to Formula (5), as blue crystals. λmax: 629 nm (inan aqueous solution).

(2) Synthesis of copper phthalocyanine tetrasulfonic acid chloride (asubstitution type at the β-position; a compound represented by Formula(6) wherein M is copper)

Into 79 parts of chlorosulfonic acid, 9.8 parts of copper phthalocyaninetetrasulfonic acid tetrasodium salt were gradually added while stirringat not higher than 60° C., and reacted at 120° C. for 4 hours, cooled to80° C., dropwise added 47.6 parts of thionyl chloride over 30 min, andreacted at 80° C. for 2 hours, then at 90° C. for one hour. The reactionsolution was cooled to not higher than 30° C., and slowly poured into700 parts of ice water. Dedeposited crystals were filtered, and washedwith 200 parts of a 2% aqueous solution of hydrochloric acid cooled withice to obtain 35.2 parts of a wet cake of copper phthalocyaninetetrasulfonic acid chloride.

(3) Synthesis of an objective compound (a compound substituted at theβ-position)

Into 100 parts of ice water, 17.6 parts of the wet cake of copperphthalocyanine tetrasulfonic acid chloride obtained in (2) were added,and suspended by stirring. After 10 min, a 28% aqueous ammonium wasadded dropwise thereto while maintaining them at not higher than 5° C.,and pH thereof was adjusted to 9.0. Then, an aqueous solution obtainedby dissolving 1.3 parts of taurine into 50 parts of water was pouredinto said suspension. The reaction was conducted at 10° C. for 2 hours,20° C. for 2 hours, and then at 50° C. for one hour while maintaining pHof 9.0 by adding a 28% ammonium aqueous solution. Water was addedthereto to adjust the solution amount to 200 parts, and 30 parts ofsodium chloride was added therein to precipitate crystals. Thusprecipitated crystals were filtrated to separate them and washed with200 parts of a 15% aqueous solution of sodium chloride to obtain 44.3parts of a wet cake. Again, all of the wet cake was dissolved in waterand whole amount was adjusted to 200 parts. After raising temperature to60° C., 10 parts of sodium chloride were added into the resultantsolution. The solution was adjusted pH thereof to 2 by the addition of a35% aqueous solution of hydrochloric acid to deposit crystals. Thusdeposited crystals were filtrated, then washed with 100 parts of a 5%aqueous solution of sodium chloride to obtain 31.8 parts of a wet cakeof the compound represented by No. 1.

The wet cake obtained of 31.8 parts was added into 260 parts ofmethanol, after addition of 13 parts of water, stirred at 60° C. for onehour to make suspension, filtered, washed with methanol, and dried toobtain 4.3 parts of blue crystals.

This colorant has not less than 75% of a compound substituted at theβ-position, λmax of 603.0 nm in water and solubility of 10% (in water atpH 9.0). By estimation from the reaction and the charged amount of a rawmaterial, it is a compound of Formula (8) (substituted position is notspecified and shown as a free acid form), wherein m is 2 and n is 2.However, as a result of analysis with a liquid chromatograph massanalyzer, a sulfonic acid group was also confirmed, therefore, byconsidering other analyzing results also, value of l (a sulfonic acidgroup) is supposed to be about 0.3, and value of n (a substitutedsulfamoyl group) is supposed to be 0.3 to 2, and therefore the residueis m (an unsubstituted sulfamoyl group), and the total of l, m and n is4 are thought to be close to an actual fact.

Example 1-2 Evaluation of an Ink

(A) Preparation of an Ink

An ink was obtained by mixing and dissolving each component as describedin Table 6 below, and by filtration with a 0.45 μm membrane filter(manufactured by Advantec Co., Ltd.). In this connection, ion-exchangedwater was used as water. Water and caustic soda (a pH adjustor) wereadded to make pH of an ink to 9, and make total amount thereof to 100parts. As for an ink, an ink using a compound of Example 1-1 wasreferred to as C-1. TABLE 6 A compound obtained in Example 1-1 1.3 partsWater + Caustic soda 79.6 parts Glycerin 5.0 parts Urea 5.0 partsN-methyl-2-pyrrolydone 4.0 parts IPA (Isopropyl alcohol) 3.0 parts Butylcarbitol 2.0 parts Surfinol 104PG50 (Trade name: manufactured 0.1 partsby Nissin Chemical Co., Ltd.) Total 100.0 parts

As a Comparative Example, a colorant for ink-jet recording generallyused as Direct Blue 199, product name: Projet Cyan 1 (manufactured byAbesia Chemical Co., Ltd.: Comparative Example 1) and a phthalocyaninecompound synthesized and purified by a method as described in Example 1of the above-described Reference 8 (Comparative Example 2) were preparedin the same method so that the same printing density was obtained onprinting as with an ink of Example 1-1 in Table 6. An ink using aproduct of Comparative Example 1 was referred to as C-A, and an inkusing a product of Comparative Example 2 was referred to as C-B.

(B) Ink-Jet Printing

Using an ink-jet printer (trade name BJ S630 manufactured by CanonInc.), ink-jet printing was conducted on two types of Professional PaperA (a high quality professional paper, HR-101S manufactured by CanonInc.) and Professional Paper B (hp premier professional paper forink-jet printing, Q1948A manufactured by Hewlett Packard Co.).

(C) Evaluation of a Recorded Image

1. Evaluation of Hue

Measurement of hue of a recorded print image was conducted bycolorimetry of a recorded paper using a calorimetric system (GRETAGSPM50: manufactured by GRETAG Co., Ltd.), and a* and b* values weremeasured within the range of 40 to 80 of L* of a printed matter. Theresults were evaluated by 3 stages based on definition of preferable a*value being −60 to −20 and preferable b* value being −60 to −20.

∘: both a* and b* values reside in the preferable range.

Δ: only one of a* and b* values resides in the preferable range.

x: both a* and b* values reside outside of the preferable range.

2. Light Fastness Test

A test piece of a recorded print image was irradiated for 50 hours atlight intensity of 0.36 W/m², under conditions of temperature of 24° C.and humidity of 60% RH in a vessel, using a xenon weatherometer (Type:Ci4000 manufactured by ATLAS Co., Ltd.). After the test, in the range ofreflection density (D value) of 0.90 to 1.10, reflection densitiesbefore and after the test were measured using the above-describedcolorimetric system. After the measurement, residual ratio of colorantswas calculated by (reflection density after testing/reflection densitybefore testing)×100 (%), and evaluated by 3 stages:

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 50 to 70%; and

x: residual ratio of lower than 50%.

3. Ozone Fastness

A test piece of a recorded print image was exposed for 3 hours at ozoneconcentration of 12 ppm, at temperature of 24° C. and at humidity of 60%RH in a vessel, using an ozone weatherometer (Type: OMS-H manufacturedby Suga Testing Machine Co., Ltd.). After the test, in the range ofreflection density (D value) of 0.90 to 1.10, reflection densitiesbefore and after the test were measured using the above-describedcolorimetric system. After the measurement, residual ratio of colorantswas calculated by (reflection density after testing/reflection densitybefore testing)×100 (%), and evaluated by 3 stages:

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 40 to 70%; and

x: residual ratio of lower than 40%.

4. Moisture Fastness

A test piece of a recorded print image was stored for 3 days attemperature of 50° C. and at humidity of 90% RH in a vessel, using athermo-hygrostat (manufactured by Ouyogiken-Sangyosya Co., Ltd.). Afterthe test, bleeding of a test piece was visually evaluated by 3 stages:

∘: bleeding is not confirmed;

Δ: slight bleeding is confirmed; and

x: much bleeding is confirmed.

Concerning recorded printing images with an ink (C-1) using a compoundobtained in Example 1-1, evaluation of hue and test results of lightfastness, ozone fastness and moisture fastness thereof are shown inTable 7 (Professional Paper A) and Table 8 (Professional Paper B). TABLE7 Evaluation result of an ink: Professional Paper A Ink No. Hue LightFastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

TABLE 8 Evaluation result of an ink: Professional Paper B Ink No. HueLight Fastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

As apparent from Tables 7 and 8, a cyan ink using a compound of thepresent invention has excellent hue, along with excellent lightfastness, ozone fastness and moisture fastness. It is apparent that ithas particularly excellent ozone fastness.

Example 1-3 An Ink Set

In an ink-jet printer (trade name: BJ F850 manufactured by Canon Inc.)having a cyan ink set provided with two concentrations of a light cyanand a dark cyan, C-1 as a light cyan ink and a genuine cyan inkmanufactured by Canon Inc. as a dark cyan ink, were mounted and ink-jetprinting was conducted on two types of Professional Paper A (a highquality professional paper, HR-101S manufactured by Canon Inc.) andProfessional Paper B (hp premier professional paper for ink-jetprinting, Q1948A manufactured by Hewlett Packard Co.). As to printingresult, there was no generation of dot deletion, and satisfactoryclear-prints even as full-colored image printing could be obtained. Asthe result, it was confirmed that an ink according to the presentinvention can be used in an ink-jet printer having a cyan ink setprovided with two concentrations of a light cyan and a dark cyan.

Example 2-1

(1) Sulfophthalocyanine substituted at the β-position was obtainedaccording to Example 1 described in the Patent Literature 8.

To a four-necked flask provided with a cooling tube, 40 parts ofsulfolane was added, and temperature thereof was raised to 180° C. inone hour. Therein, 40 parts of 4-sulfophthalic acid, 4.5 parts ofammonium chloride, 55 parts of urea, 0.5 parts of ammonium molybdate,and 6 parts of copper (II) chloride were added, and stirred at the sametemperature for 6 hours. After the reaction solution was cooled to 40°C., an objective product was filtered with Nutsche, and washed with 400parts of methanol. Subsequently, 300 parts of water was added to a wetcake obtained, and pH thereof was adjusted to 10 using a 48% aqueoussolution of NaOH, and stirred at 80° C. for one hour. A 35% aqueoussolution of hydrochloric acid was added thereto while stirring, to makepH 3, then gradually added thereto 80 parts of sodium chloride. Crystalsdeposited were filtered off and washed with 150 parts of a 20% aqueoussolution of sodium chloride to obtain 90 parts of a wet cake. Then, 210parts of methanol was added thereto, and stirred for one hour, separateddeposited crystal by filtration, washed with 300 parts of a 70% aqueoussolution of methanol and dried to obtain 22.9 parts of phthalocyaninesubstituted at the β-position, wherein M′ is a sodium salt, as bluecrystals. λmax: 629 nm (in an aqueous solution).

(2) Into 69.1 parts of chlorosulfonic acid, 9.84 parts of a compoundobtained in (1) was gradually added while stirring at not higher than70° C. and reacted at 120° C. for 4 hours. After the reaction, thereaction solution obtained by cooling was poured into 300 parts of icewater to decompose residual chlorosulfonic acid. Deposited crystal wasfiltrated, washed with 67 parts of ice water to obtain 37.2 parts of awet cake.

(3) Into 130 parts of ice water, 37.2 parts (0.01 mol) of the wet cakeobtained in (2) was added, and stirred for 30 minutes at not higher than5° C. By adding ammonia water, pH was adjusted at 10 to 10.5 whilemaintaining temperature at 0 to 5° C. Reaction was continued for 1 hourunder this condition, then 1 hour at 25° C. and further 1 hour at 60° C.while maintaining pH at 9.5 to 10.0 to obtain 360 parts of a reactionmixed solution. This reaction mixture was adjusted to temperature of 60°C. and pH of 7.0 by a 10% HCl solution and 72 parts of sodium chloridewas gradually added. After stirring for 30 minutes, deposited crystalwas filtrated to obtain 40.2 parts of a wet cake.

(4) Into 200 parts of methanol was added 40.2 parts of the wet cakeobtained in (3) while stirring and continued stirring for 1 hour.Crystals were filtered, washed with 50 parts of methanol to obtain a wetcake. Thus obtained wet cake was added again into 150 parts of methanoland the wet cake obtained (18.5 parts) was dried to obtain 9.3 parts ofa colorant mixture. This colorant mixture had not lower than 75% of theβ-substituted compound and λmax of 605.5 nm in water and contained Cl⁻:not higher than 0.1%, SO₄ ²⁻: not higher than 0.1%, Fe: not higher than100 ppm, Zn: not higher than 100 ppm and Ca: not higher than 200 ppm.

Example 2-2

Similarly as in Example 2-1, chlorination was carried out in 46.0 useparts of chlorosulfonic acid to obtain 36.0 parts of a wet cake, acolorant mixture having lower conversion ratio to a sulfamoyl group thanin the colorant mixture obtained in Example 1. This mixture was thensubjected to reaction with ammonia water and purification similarly asin Example 2-1 to obtain 9.1 parts of a dry substance (a colorantmixture). This colorant mixture has not lower than 75% of theβ-substituted compound and λ max of 605.5 nm in water and contained Cl⁻:not higher than 0.1%, SO₄ ²⁻: not higher than 0.1%, Fe: not higher than100 ppm, Zn: not higher than 100 ppm and Ca: not higher than 200 ppm.

Example 2-3

Similarly as in Example 2-1, chlorination was carried out in 34.6 useparts of chlorosulfonic acid to obtain 36.6 parts of a wet cake, acolorant mixture having lower conversion ratio to a sulfamoyl group thanin the colorant mixture obtained in Example 2. This mixture was thensubjected to reaction with ammonia water and purification similarly asin Example 2-1 to obtain 8.8 parts of a dry substance (a colorantmixture). This colorant mixture has not lower than 75% of theβ-substituted compound and λmax of 611.0 nm in water and contained Cl⁻:not higher than 0.1%, SO₄ ²⁻: not higher than 0.1%, Fe: not higher than100 ppm, Zn: not higher than 100 ppm and Ca: not higher than 200 ppm.

Example 2-4

(1) Into 46.0 parts of chlorosulfonic acid, 9.84 parts of a compoundobtained in Example 2-1(1) was gradually added while stirring at nothigher than 70° C. and reacted at 120° C. for 4 hours. After cooling thereaction solution down to 80° C., 9.52 parts of thionylchloride wasadded dropwise and reacted for 2 hours at the same temperature. Thereaction solution obtained was poured into 200 parts of ice water todecompose residual chlorosulfonic acid and thionylchloride. Afterremoving sulfurous acid in a solution by hydrogen peroxide water,deposited crystal was filtrated, washed with 67 parts of ice water toobtain 35.0 parts of a wet cake.

(2) Similarly as in Example 2-1 (3), the wet cake was reacted withammonia water and purified similarly to obtain 10.4 parts of a driedsubstance (a colorant mixture). This colorant mixture had not lower than75% of the β-substituted compound and λmax of 603.0 nm in water and,taking into consideration of other analysis results also, sulfamoylconversion ratio was equivalent to that of a colorant mixture obtainedin Example 1.

This colorant mixture contained Cl⁻: not higher than 0.1%, SO₄ ²⁻: nothigher than 0.1%, Fe: not higher than 100 ppm, Zn: not higher than 100ppm and Ca: not higher than 200 ppm.

Example 2-5 Evaluation of an Ink

(A) Preparation of an Ink

An ink was obtained by mixing and dissolving each component as describedin Table 9 below, and by filtration with a 0.45 μm membrane filter(manufactured by Advantec Co., Ltd.). In this connection, ion-exchangedwater was used as water. Water and caustic soda (a pH adjustor) wereadded to make pH=8-10 of an ink, and make total amount thereof to 100parts. An ink using an colorant mixture of Example 2-1 was referred toas C-1 and inks using Examples 2-2 to 2-4 were referred to as C-2 toC-4, respectively. TABLE 9 Each colorant mixture obtained in Examples0.9 parts 2-1 to 2-4 Water + Caustic soda 80.6 parts Glycerin 5.0 partsUrea 5.0 parts N-methyl-2-pyrrolydone 4.0 parts IPA (Isopropyl alcohol)3.0 parts Butyl carbitol 2.0 parts Surfinol 104PG50 (manufactured byNissin 0.1 parts Chemical Co., Ltd.) Total 100.0 parts

As a Comparative Example, a colorant for ink-jet recording generallyused as Direct Blue 199, product name: Projet Cyan 1 (manufactured byAbesia Chemical Co., Ltd.: Comparative Example 1) and a colorant mixturesynthesized and purified by a method as described in Example 1 of theabove-described Patent Reference 8 (Comparative Example 2) wereformulated for inks in the same method so that the same printing densitywas obtained on printing as with inks C-1 to C-4. An ink using a productof Comparative Example 1 was referred to as C-A, and an ink using acolorant mixture of Comparative Example 2 was referred to as C-B.

(B) Ink-Jet Printing

Using an ink-jet printer (trade name BJ S630 manufactured by CanonInc.), ink-jet printing was conducted on two types of Professional Paper(a high quality professional paper, HR-101 manufactured by Canon Inc.)and Glossy Paper (a professional photo paper PR-101 manufactured byCanon Inc.).

(C) Evaluation of a Recorded Image

1. Evaluation of Hue

Measurement of hue of a recorded print image was conducted bycolorimetry of a recorded paper using a colorimetric system (GRETAGSPM50: manufactured by GRETAG Co., Ltd.), and a* and b* values weremeasured within the range of 50 to 90 of L* of a printed matter. Theresults were evaluated by 3 stages based on definition of preferable a*value being −50 to −10 and preferable b* value being −50 to −10.

∘: both a* and b* values reside in the preferable range.

Δ: only one of a* and b* values resides in the preferable range.

x: both a* and b* values reside outside of the preferable range.

2. Light Fastness Test

A test piece of a recorded print image was irradiated for 50 hours atlight intensity of 0.36 W/m², under conditions of temperature in avessel of 24° C. and humidity of 60% RH, using a xenon weatherometer(Type: Ci4000 manufactured by ATLAS Co., Ltd.). After the test, in therange of reflection density (D value) of 0.70 to 0.85, reflectiondensities before and after the test were measured using the colorimetricsystem. After the measurement, residual ratio of colorants wascalculated by on (reflection density after testing/reflection densitybefore testing)×100 (%), and were evaluated by 3 stages:

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 50 to 70%; and

x: residual ratio of lower than 50%.

3. Ozone Fastness

A test piece of a recorded print image was exposed for 3 hours at ozoneconcentration of 12 ppm, at temperature of 24° C. and at humidity of 60%RH in a vessel, using an ozone weatherometer (Type: OMS-H manufacturedby Suga Testing Machine Co., Ltd.). After the test, in the range ofreflection density (D value) of 0.70 to 0.85, reflection densitiesbefore and after the test were measured using the above-describedcolorimetric system. After the measurement, residual ratio of colorantswas determined by calculation based on (reflection density aftertesting/reflection density before testing)×100 (%), and evaluationresults were ranked by 3 stages:

∘: residual ratio of not lower than 70%;

Δ: residual ratio of 40 to 70%; and

x: residual ratio of lower than 40%.

4. Moisture Fastness

A test piece of a recorded print image was stored for 3 days attemperature of 50° C. and at humidity of 90% RH in a vessel, using athermo-hygrostat (manufactured by Ouyogiken-Sangyosya Co., Ltd.). Afterthe test, bleeding of a test piece was visually evaluated by 3 stages:

∘: bleeding is not confirmed;

Δ: slight bleeding is confirmed; and

x: much bleeding is confirmed.

Concerning recorded printing images with inks (C-1 to C-4) usingcolorant mixtures obtained in Examples 2-1 to 2-4, evaluation of hue andtest results of light fastness, ozone fastness and moisture fastnessthereof are shown in Table 10 (Professional Paper) and Table 11 (GlossyPaper). TABLE 10 Evaluation result of an ink: Professional Paper Ink No.Hue Light Fastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-2 ∘ ∘ ∘ ∘ C-3 ∘ ∘∘ ∘ C-4 ∘ ∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

TABLE 11 Evaluation result of an ink: Glossy Paper Ink No. Hue LightFastness Ozone F. Moisture F. C-1 ∘ ∘ ∘ ∘ C-2 ∘ ∘ ∘ ∘ C-3 ∘ ∘ ∘ ∘ C-4 ∘∘ ∘ ∘ C-A ∘ ∘ x ∘ C-B ∘ ∘ x ∘

As apparent from Tables 10 and 11, a cyan ink using a colorant mixtureof the present invention has excellent hue, along with excellent lightfastness, ozone fastness, and moisture fastness. It is apparent that ithas particularly excellent ozone fastness.

Example 2-6 (an ink set)

In an ink-jet printer (trade name: BJ F850 manufactured by Canon Inc.)having a cyan ink set provided with two concentrations of a light cyanand a dark cyan, C-1 as a light cyan ink, and a genuine cyan inkmanufactured by Canon Inc., as a dark cyan ink, were mounted, andink-jet printing was conducted on two types of Professional Paper (ahigh quality professional paper, HR-101 manufactured by Canon Inc.) andGlossy Paper (a professional photo paper PR-101 manufactured by CanonInc.). As to printing result, there was no generation of dot deletion,and satisfactory clear-prints as even as full-colored image printingcould be obtained. As the result, it was confirmed that an ink accordingto the present invention can be used in an ink-jet printer having a cyanink set provided with two concentrations of a light cyan and a darkcyan.

INDUSTRIAL APPLICABILITY

An ink using a phthalocyanine compound of the present invention has afavorable hue as a cyan ink, and the like, and excellent light fastness,ozone fastness and moisture fastness. Further, it does neither exhibitcrystal deposition, nor change in physical properties, nor change incolor after a long period of storage, and thus storage stability isfavorable. Further, by combined use with other magenta ink and yellowink, color tone in a broad visible region can be obtained. Therefore,the ink using a phthalocyanine colorant according to the presentinvention, especially a cyan ink, is extremely useful as an ink used forink-jet recording.

1. A phthalocyanine colorant represented by Formula (1):

[in Formula (1), M represents a hydrogen atom, a metal atom, a metaloxide, a metal hydroxide, or a metal halide; R₂, R₃, R₆, R₇, R₁₀, R₁₁,R₁₄ and R₁₅ each independently represent an unsubstituted sulfamoylgroup represented by Formula (2), a substituted sulfamoyl grouprepresented by Formula (3), or a hydrogen atom, provided that at leastone of R₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅ is an unsubstitutedsulfamoyl group, and at least one thereof is a substituted sulfamoylgroup represented by Formula (3); and R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ andR₁₆ represent hydrogen atoms; the sum of a number of an unsubstitutedsulfamoyl group and a total number of a substituted sulfamoyl group is 2to 4, and a number of an unsubstituted sulfamoyl group is 1 to 3 and anumber of a substituted sulfamoyl group is 1 to 3.]:

, in Formula (3), R₁₇ and R₁₈ each independently represent a hydrogenatom, a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heterocyclic group, and a substituted or unsubstitutedalkenyl group; R₁₇ and R₁₈ may form a ring by bonding together exceptwhen both R₁₇ and R₁₈ represent a halogen atom; and at least one of R₁₇and R₁₈ has an ionic and hydrophilic group as a substituent.
 2. Thephthalocyanine colorant according to claim 1, wherein Formula (1)according to claim 1 wherein M is Cu, is represented by Formula (4):

, in Formula (4), R₁ to R₁₆ mean the same as in Formula (1).
 3. Thephthalocyanine colorant according to claim 1 or claim 2, wherein in eachof combinations of R₂ and R₃, R₆ and R₇, R₁₀ and R₁₁, and R₁₄ and R₁₅,one member of each combination is a hydrogen atom, and the other is anunsubstituted sulfamoyl group represented by Formula (2), a substitutedsulfamoyl group represented by Formula (3) or a hydrogen atom, and amongR₂, R₃, R₆, R₇, R₁₀, R₁₁, R₁₄ and R₁₅, at least one is an unsubstitutedsulfamoyl group and at least one is a substituted sulfamoyl grouprepresented by Formula (3).
 4. The phthalocyanine colorant according toany one of claims 1 to 3, wherein R₁₇ and R₁₈ each independentlyrepresent a hydrogen atom, an alkyl group (which may be substituted witha substituent selected from a group consisting of a sulfonic acid group,a carboxyl group, a hydroxyl group, an alkoxyl group, a dialkylaminogroup, an arylamino group, an aryl group, a halogen atom and a cyanogroup), a phenyl group (which may be substituted with one or moresubstituents selected from a group consisting of a sulfonic acid group,a carboxyl group, a hydroxyl group, a dialkylamino group, an arylaminogroup, an acetylamino group, a ureido group, an alkyl group, an alkoxylgroup, a nitro group, a cyano group, a heterocyclic group and a halogenatom), a naphthyl group (which may be substituted with a sulfonic acidgroup or a hydroxyl group), a benzyl group (which may be substitutedwith a sulfonic acid group) and a phenethyl group (which may besubstituted with a sulfonic acid group).
 5. The phthalocyanine colorantaccording to any one of claims 1 to 3, wherein R₁₇ is a hydrogen atom, acarboxyl(C1 to C5)alkyl group, a (C1 to C5)alkyl group, a hydroxyl(C1 toC5)alkyl group and a sulfo(C1 to C5)alkyl group; and R₁₈ is a phenylgroup having a sulfo(C1 to C5)alkyl group, a carboxyl(C1 to C5)alkylgroup, a sulfonic acid group, a carboxyl group or a hydroxyl group, abenzotriazolyl group substituted with a phenyl group having adi(sulfo(C1 to C5)alkyl) amino(C1 to C5)alkyl group, a sulfonic acidgroup, a carboxyl group or a hydroxyl group, a phenyl group substitutedwith a benzotriazol group having a sulfonic acid group, a carboxyl groupor a hydroxyl group, a naphthyl group having a sulfonic acid group or ahydroxyl group, a uracil group having a sulfonic acid group, a carboxylgroup or a hydroxyl group, a triazol group having a sulfonic acid group,a carboxyl group or a hydroxyl group, a thiazolyl group having asulfonic acid group, a carboxyl group or a hydroxyl group, abenzothiazolyl group having a sulfonic acid group, a carboxyl group or ahydroxyl group, a pyridine group having a sulfonic acid group, acarboxyl group or a hydroxyl group, and a benzimidazolyl group having asulfonic acid group, a carboxyl group or a hydroxyl group.
 6. Thephthalocyanine colorant according to claim 1, wherein content of thecolorant represented by Formula (1) is at least not less than 60% basedon total colorants.
 7. The phthalocyanine colorant according to any oneof claims 1 to 5, wherein the colorant represented by Formula (1) isobtained by subjecting the phthalocyanine colorant represented byFormula (5):

(in Formula (5), respectively, M represents a hydrogen atom, a metalatom, a metal oxide or a metal halide; L represents a proton, analkaline metal ion, an alkaline earth metal ion and an onium ion of anorganic amine or ammonium ion; and a, b, c and d are 0 or 1, providedthat the sum thereof is an integer of 2 to 4) or a salt thereof toreaction with a chlorinating reagent to convert a sulfonic acid group toa chlorosulfonyl group and subsequent reaction with an amidating reagentin the presence of an organic amine.
 8. A phthalocyanine colorantobtained by subjecting 4-sulfophthalic acid derivatives themselves toreaction with a metallo compound in the presence of the metallocompound, followed by subjecting thus obtainedsulfometallophthalocyanine compound or a salt thereof to reaction with achlorinating reagent to convert a sulfonic acid group to achlorosulfonyl group and subsequent reaction with an amidating reagentand an organic amine.
 9. An ink characterized by comprising thephthalocyanine colorant according to any one of claims 1 to 8, as acolorant component.
 10. The ink according to claim 9, wherein an organicsolvent is contained.
 11. The ink according to claim 9 or claim 10,which is used for ink-jet recording.
 12. An ink set characterized, in anink-jet printer using not less than 2 kinds of cyan inks with differentcolorant density, by using, as at least one kind therefore, the inkaccording to any one of claim 9 or
 11. 13. An ink-jet recording methodcharacterized by using the ink according to any one of claims 9 to 11 orthe ink set according to claim 12, in an ink-jet recording methodwherein the recording is carried out onto a recording material bydischarging ink droplets in response to recording signals.
 14. Theink-jet recording method according to claim 13 wherein the recordingmaterial is an information transmission sheet.
 15. Then ink-jetrecording method according to claim 14 wherein the informationtransmission sheet is a surface treated sheet having an ink imagereceiving layer containing white inorganic pigment particles on acarrier.
 16. A container containing the ink or the ink set according toany one of claims 9 to
 12. 17. An ink-jet printer having the containeraccording to claim
 16. 18. A colored product colored with the ink or theink set according to any one of claims 9 to
 12. 19. A method forproduction of a phthalocyanie colorant characterized by subjecting4-sulfophthalic acid derivatives to reaction with themselves orsubjecting a 4-sulfophthalic acid derivative to reaction with a phthalicacid (phthalic anhydride) derivative in the presence of a coppercompound, followed by subjecting thus obtained compound or a saltthereof to reaction with a chlorinating reagent to convert a sulfonicacid group to a chlorosulfonyl group and subsequent reaction with anamidating reagent and an organic amine.
 20. A phthalocyanine colorantwherein, in the phthalocyanine colorant represented by the followinggeneral Formula (9):

(wherein M represents a hydrogen atom, a metal atom, a metal oxide, ametal hydroxide or a metal halide; l includes 0 and smaller than 1; m isnot smaller than 1 and not larger than 3.7; n is not smaller than 0.3and not larger than 3; sum of l, m and n is not smaller than 2 and notlarger than 4; R₁₇ and R₁₈ each independently represent a hydrogen atom,a substituted or unsubstituted alkyl group, a substituted orunsubstituted cycloalkyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted heterocyclic group, and a substituted or unsubstitutedalkenyl group; R₁₇ and R₁₈ may form a ring by bonding together, providedthat except when both R₁₇ and R₁₈ represent a hydrogen atom; and atleast one of R₁₇ and R₁₈ has an ionic and hydrophilic group as asubstituent.), a β-substituted compound is not less than 60% and anα-substituted compound is not more than 40%.
 21. A mixture of colorantsrepresented by the following general Formula (10):

{wherein R₂′, R₃′, R₆′, R₇′, R₁₀′, R₁₁′, R₁₄′ and R₁₅′ eachindependently represent an unsubstituted sulfamoyl group (—SO₂NH₂), asulfone group (—SO₃M′) or a hydrogen atom, provided that at least one ofR₂′, R₃′, R₆′, R₇′, R₁₀′, R₁₁′, R₁₄′ and R₁₅′ is an unsubstitutedsulfamoyl group; R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ and R₁₆ represent hydrogenatoms; and M′ represents a proton, an alkaline metal ion, an alkalineearth metal ion and an onium ion of an organic amine or ammonium ion.}22. A mixture of colorants obtained by subjecting 4-sulfophthalic acidderivatives, or a 4-sulfophthalic acid derivative and a phthalic acid(phthalic anhydride) derivative to reaction with a copper compound inthe presence of a copper compound, followed by subjecting thus obtainedcompound or a salt thereof to reaction with a chlorinating reagent toconvert a sulfonic acid group to a chlorosulfonyl group and subsequentreaction with an amidating reagent.